Metallisable polyazo dyestuffs and the complex copper compounds thereof



United State Patent METALLISABLE POLYAZO-DYESTUFFS AND THE COMPLEXCOPPER COMPOUNDS THEREOF Rudolf Durig, Basel, and Werner Bossard, Riehen, near Basel, Switzerland, 'assignors to J. R. Geigy A.-G.,' Basel, Switzerland, a Swiss firm r p No Drawing. Application June 17, 1957' p 7 SerialNo. 666,239 7 Claims priority, application Switzerland August 2, 1 956 1 Claims. (Cl. 260-148) The present inventionjconcerns metallisable polyazo dyestufis and the complex copper compounds thereof, as well as the production of these dyestuffs. It also con cerns the use thereof for the fast dyeing of cellulosic material in pure blue shades.

, It has been found that valuable blue polyazo dyestuffs are obtained if tetrazotised 4'. 4'-diaminodipheny1,compounds which, in the ortho-position to the diazonium groups, contain substituents which are capable of form ing the metal complex or groups which can be converted into such, are coupled-with two molecules of hydroxynaphthalene sulphonic acids which can be further sub- :stituted, of whichat least one molecule is al-amino-8- hydroxynaphthalene-6-sulphonic acid substituted at the amino group, and the dyestuifs obtained are treated either in substance or on the fibre with agents giving ofi copper.

In the metal-free condition, the new polyazo dyestufi I correspond to the general formula: I

x x no NHR (ze-mmn-a-mucc-umm SOsH wherein A represents the radical of a hydroxynaphthalene sulphonic acid bound to the azo linkage in o-position to the hydroxyl group,

ice

. 2 phenyl and, with particular dimethoxydiphenyl.

Of the hydroxynaphthalene sulphonic acids coupling in the ortho-position to a hydroxyl group'which may possibly be substituted, which are used in the present groups are the acetyl, chloracetyl, methoxy acetyl, phenoxy acetyl groups, benzoyl, as well as chlorinated and alkylated benzoyl groups and finally carbomethoxy and carboethoxy groups.

If, in the present process in the formation of unsym metrical dyestuffs, only 1 mol of the L-amino-8-hydroxynaphthalene-G-sulphonic acid above mentioned is used per mol of tetrazonium compound, then one mol of an unsubstituted hydroxynaphthalene mono-, dior tri-sulphonic acid or one mole of another arninohydroxynaphthalene sulphonic acid which may possibly be further substituted, is used as second component. A condition of the present process is that in this second azo component, the o-position to the'hydroxyl group must be free also and capable ofbeing coupled. Examples of unsubstituted hydroxynaphthalene sulphonic acids are lhydroxynaphthalene-3- or -4-sulphonic acid, 2-hydroxynaphthalene-6-sulphonic acid, 1-hydroxynaphthalene-3.6-, -3.8- and -4.8-disulphonic acids, 2-hydroxynaphthalene-3.6- and -6.8-disulphonic acids and l-hydroxynaphthalene- 3,6,8-trisulphonic acid and examples of substituted hydroxynaphthalenesulphonic acids are 1.8-dihydroxynaph- B represents a mononuclear radical of the benzene series,

X represents a metallisable group, I

R represents a member selected from the group consist-1 ing of lower alkyl mononuclear aryl and acyl radicals,

n represents the numerals 0 and l. a

The copper complex compounds of the formula:

SOaH

wherein A and R have the meanings given above, are particularly valuable. 1

Examples of 4.4-diaminodiphe nyl compounds containing substituents in the ortho-position' to the aminogroups h which are capable of forming themetal complex are 4.45;; diaminodiphenyl-3.3-dicarboxylic acid and 4.4'-diarhino- 3.3-dihydroxydiphenyl. Etherified derivatives of the latter with possibly substituted lower alkyl groupscan also be used as such in the process according to the present invention, e.g. 4.4-diamino-3.3-dicarboxymethoxydithalene 3 .6-disulphonic acid and l-hydroxy-S-ethoxyor -8-chloronaphthalene-3.6-disulphonic acid.. Both amino hydroxynaphthalene sulphonic acids themselves as well as the alkyl, cycloalkyl, aralkyl, aryl and acyl derivatives thereof substituted at the amino groups are 'used as aminated derivatives, e.g. N-acetyl, N-benzoyl and N-"' phenyl derivatives of 1-amino-8-hydroxynaphthalene-3.6-

and 4.6- disulphonic acid, of 1- or '2-amino-5 -hydroxynaphthalene-7-sulphonic acid, of 2-amino-6-hydroxyriaphthalene-S-sulphonic acid and of 2-amino-8-hydroxy naphthalene-fi-sulphonic acid. In addition amino-hydroxyriaphthalene sulphonic acids containing aryl azo groups can be named, such as are obtained for example by acid coupling of diazonium compounds of the benzene seriesvwith such amino hydroxynaphthalene sulphonic ;acids, the ortho-positions to the amino and hydroxy groups of which are both free and capable of being coupled. Thesecomponents containing azo groups are particularly suitable for the production of polyazo dyestuffs which dye cellulose material in navy blue shades.

Of the azo dyestuffs which canbe produced according to the process according to the present invention,

those which contain 1 mol of a l-hydroxynaphthalene sulphonic acid, examples of which have been given above,

"and '1 mol of a 1-acyla1nino-8-hydroxynaphthalene-6-su1- phonic acid to 1 mol of tetrazonium'compound are particularly distinguished by their very good fastness properi ties. Of particular technical value arelthe complex copper compounds from diazotised 4.4'-diamino-3.3'-di methoxydipheny1 coupled with 1 mol of a 'l-hydroxynaphthalene sulphonic acid and 1 mol of a l-acylamino- 8-hydroxynaphthalene-6-sulphonic acid, dyestuffs having a total of three sulphonic acid groups being preferred because of their solubility.

Patented Mar. 8,1960

advantage, 4.4'-diamino-3.3'-

The tetrazoniurn compounds are coupled with the hy- In the form of their alkali and ammonium salts, the

new polyazo dyestufis are dark powders which dissolve in water with a blue colour and dye cellulose fibres from liquors containing Glaubers salt in blue shades. The dyeings are fixed fast to light and wet by after treatment with agents giving oif'copper. Of particular interest are the complex copper compounds which can beproduced by known methods from the metal-free polyazo dyestufis according to the present invention. They dye cellulose material such as cotton and regenerated cellulose fibres in very pure, reddish to greenish blue shades which have remarkable fastness properties, in particular very good fastness to acids. No undesirable change in the shade and practically no injurious effect on the light fastness of the dyeings is noticeable on subjecting the cellulose dyeings later to anti-crease processing. The complex copper compounds, in particular those which have ail-' ready been mentioned as valuable groups, have a strong afiinity to cellulose fibres. parison with already known, similar polyazo dyestuffs, they have however, very good levelling power.

The following examples serve to illustrate the inven tion without limiting it in any way. In these examples, the temperatures are given in degrees centigrade and, where not otherwise stated, parts are given as parts by weight.

Example 1 At the same time, in cornti) until the coupling is complete.

raised to 90-95 for 15,920. hours 24.4 parts of 4.4'-diamino-3.3 -dimethoxydiphenyl are etrazotised in. theus al wayand. oured at 0:5. into. a solution of 30.4 parts of l-hydroxynaphthalene-l8- disulphonic acid and parts of sodium carbonate in 1000 parts of Water. The diazo-monoazo dyestufi precipitates completely after a short time and no more tetrazonium compound, can be traced. A soda alkaline solution of 28.1 parts of l-acetylaminoe8ehydroxynaphthalene- 6-sulphonic acid is then added and the whole' is stirred The disazo, dyestuffob: tained in. this wayis precipitated with sodium chloride, filtered oil and again dissolved in 2500' parts of water at -85 400 parts'ofa copper oxide/ammonia solution which contains 50 parts of crystallised copper sulphate and parts of concentrated aqueous ammonia, are then added and the whole is stirred at this temperature for 4-5 hours. After the addition of a further 50 parts of concentrated ammonia solutionthe temperature is T e ppe comp ex formed is precipitated with sodium chloride, filtered oil.

and dried. It is a dark powder which dissolves in water with a blue colour and draws onto cotton, linen an 4"? generated cellulose fibres excellently frorn an aqueous bath. The dyeings have very good fastne ss to light and also the shade and fastness to light are barely. influenced by. anti-crease processing.

In the following table further dyestuffs are given which are obtained in a similar manner by coupling tetrazotised 4.4 '-diamino-3.3'-dimethoxydiphenyl with the azo com: ponents in columns 1 and 3 and converting into the copper complexes.

0 NH-C OCH:

Component A Tetrazo compound OCH:

SOsH

OCH:

OCH:

Component B Shade of coppercontalnlng dyeing Blue. IITO IIIHC O 1 n1, SOgH H0 .NHCOOCH: Do.

HO l}THCOO-CH2 D0. H 'NHg CgHrno .NHGO'CH D0- I C (011;):

.HOt

A soda alkaline solution 0526.7 parts of l-ethylaminoconverted into the copper complex as described in Example 1-. The copper-containing dyestuff dyes eotton' and staple'fibre in strong blue shades which have very good fastness to light,

Some dyestuffs are given in the following table whi h are obtained infa similar manner. Their dyeings on cellulose material have also very good fastness properties.

. No. ComponentA Tatrazo compound ComponentB cgllllgligitggcodgglohrg 1 Hots 0H 7 (3on5. OCH: no l rnoanion Blue.

- 2 H038 11 OCH: 00.111v Do.

- SOsH V Hoas a Hms n; 0on3 OCH: HO NH 0cm Do.

Nlz't NH: I

SOaH Hoas 4 no on OGH; OCH: HO N11051:. Do.

QQ H018 501R 7' HOIS a no on 0011. 00th r NH Do.

NH NHa H018 SOaEi Boss 6 H501? on OCH; OCH: no Imam, D0.

1103s SOaH i I i 1 11 on lwfl OCH; Do.

I 06 Hots s0=H i B035- 8 Hots 011 com 0cm H0 ITTHCH: Do.

Hm. 'Nm

S0;H rots:

a H0;S OH 0011;. 00m no NHCH; Do.

I H:N NH]:

soul

10 H038 on V 0011-: 00H; HO NH-C2H4OH v Do.

@ Hm m1, 7

No. Component A Tetrazo compound Component B Shade of copper v q I ,1 i v V containing dyeing 11 H 8 OH it J OCH; I OCH; 7 Blue.

a q; HO NH OCH: H,N us, I

i 3' 7' HO:

Example 3 omoonN o--cuo 0-1111 0 Nncocm I l I no. son: 3 rims Asoda alkaline solution of 28.1 parts of l-acetylaminostuif is salted out and isolated. The trisazo dyestufi so 8-hydroxynaphthalene-6-sulphonic acid is poured into the obtained dyes cotton and staple fibres in navy blue shades, diazonium compound from 24.4 parts of tetrazotised 4.4- the Wet and light fastness properties of which are condiamino-3.3' dimethoxydiphenyl and 36.1 parts of 1- siderably improved by after-treatment with copper salt acetylamino-8-hydroxynaphthalene-3.6-disulphonic acid solutions.

and the whole is stirred until the coupling is complete. Similar dyestuifs are obtained if, inthe acid coupled The copper complex compound obtained therefrom by 3,0 monoazo dyestuif, the '2-aminobenzene-1-carboxylic acid the method described in Example lidyes'cellulose material I a is replaced by 2-amino-5-nitrobenzene-l-carboxylic acid direct in vivid blue shades which have very good fastness or by 5-amino-Z-hydroxybenzene-l-carboxylic acid or by to light. l 'aminobenzene, or if 1-benzoylamino-8-hydroxynaphtha- Similar dyestuffs are obtained if, in this example, the 1-acetylamino-8-hydroxynaphthalene-3.6-disulphonic acid 5 hydroxynaphthalene-6-sulphonic acid. H

Example 5 is replaced by 39.5 parts of 1-phenylamino-8-hydroxy- 27.2 parts of 4.4'-diaminodiphenyl-3.3'-dicarboxylic naphthalene 4.6-disulphonic acid orby 39.5 parts of 2- acid are tetrazotised in the usual way and poured at 0--5 a (3' sulphophenylamino) 5. evhydroxynaphthalene 7- into a solution of 56.2 parts of 1-acetylamino-8-hydroxy-' sulphonic acid or by 3- 9.5 parts of 2-(3'-sulphophenyl- 5o naphthalene-o-sulphonic acid and 70 partsof sodium amino)-8 hydroxynaphthalene-6-sulphonic acid. carbonate in 1800 parts of water. 7 The symmetrical dis- Ex m 4 no. t incocn.

. 24.4 parts'of, 4.4' diamino 3.3 dimethoxydiphenylare azo dyestuff precipitates after a short timeand can be teil'alofisefi a d P' fi at M q of Q easily isolated by the addition of a little sodum chloride. P of the monoazo dyestufi Produced an and medlum It dyes cotton and cellulose material in reddish :blue

vlei1e-6-sulphonic acid is used instead of l-acetylamino-S- omcoHN on coon H v c0011 HO IFHCOCH;

from diazotised 2 aminobenzene-l-carboxylic acid and 2- Shades wetland lightrfastness properties of which amino-5-hydroxynaphthalene-7-sulphonic acid, and parts of sodium carbonate in 1000 parts of water.. As soon as no more tetrazonium compound can be traced, a soda'ralkaline solution of 28.1. parts of l-acetylamino-S- canibe considerably improved by after coppering.

Further symmetrical dyestuifs are given in the following table which are obtained in a similar manner, the

hydroxynaphthalene6=sulphonic acid isadded and the after-coppered cotton dyeings of which also have good f whole isstirred until the-coupling is complete. The dye fastnessproperties.

No. Tetrazo compound, 1 mol Azo componenuz m'ol Shade ol eo per: containing yelng 1 C O OH O 0H Reddish blue.

no 113100- HQN NH; 7

2 HOOCCHzO OCHICOOH Greenlsh blue,

' H0 111110 0 HQN NH:

HO;S

3 1100001120 OCHSCOOH H0 N'HCOCE; Do;

HaN NH:

4 OH OH' H 0 NBC 0. CH; Blue,

011 on no z nrcoocui D0.

' Hots- Example 6 1 2 parts of a dyestuff obtained according to Examples 1, 2 or 3 are dissolved in a dyebath containing 3000 parts of water and 1 part of sodium carbonate. 100 Parts of cotton are entered at 40-50", the bath is heated within 30'minutes to 90-95", 30 parts of sodium suI- phate are added and dyeing is continued at this temperature for 45 minutes. After this time, the dyed goods are rinsed cold in the usual way and dried. The cotton. is. dyed, in this manner in clear blue shades which have. good wet fastness and very good light fastness properties;

If a dyestuff obtained according to Example 4 or 5 isused, for the dyeing, then, after rinsing, the dyed cotton is after-treated in a fresh bath for minutes at 70 with 2 parts of copper sulphate and 2 parts of acetic acid. It is then rinsed cold and dried. The wet and light fastness properties of these dyeings are considerably increased in this manner.

What we claim is:

1. A member of the group consisting of a polyazo.

dyestufi of the general formula:

NHR

wherein acyl being the radical of a lower monocarboxylic acid, n represents the numerals 0 and 1,

p and the complex copper compound thereof.

B represents a mononuclear radical of the benzene series,

X representsa metallisable group, I r R represents a member selected from the grqunconsist-ing of lower alkyl, mononuclear aryl and acyl radicals,

2. A cupriferous disazo dyestufi of the general formula:

A represents the radical of a naphthalene sulphonic acid,

the group 'O-Cu -0.- being bound to vicinal positions with respect to thea'zo group, and

Rrepresents a member selectedtfrom th'egroup consisting of lower alkyl, mononuclear aryl and acyl radicals,

D represents the radicalgofag naphthaleneidi's'ulphonic acid" bound to the: azo group. in. Zeposition and? to. the.

. 'adical of alower monocarboxylic acid. 

1. A MEMBER OF THE GROUP CONSISTING OF A POLYAZO DYESTUFF OF THE GENERAL FORMULA: 